Shallow groundwater of the huge deltaic systems of Asia like the Red River Delta in Vietnam is often enriched in inorganic arsenic (As), threatening the health of millions of residents. The massive abstraction of groundwater in these areas locally causes an irreversible mixing of arsenic-free groundwater resources with arsenic-rich groundwater. Increased concentrations of competitive anions, especially phosphate (PO43-), decrease the immobilization capacity of the sediments. During transport, the mobility of dissolved As in local aquifers is strongly influenced by adsorption to sedimentary and ubiquitously occurring iron(oxyhydr)oxides. Additionally, arsenic-rich groundwater is often enriched in reduced iron (Fe2+) as well, which is capable to react with iron(oxyhydr)oxides, thereby inducing mineral transformations. Such transformations permanently affect the arsenic adsorption and immobilization capacity of the sediments.Within the scope of this research project, the underlying mechanisms related to As transport and the resulting threat to arsenic-free groundwater resources will be characterized in cooperation with the Swiss Federal Institute of Aquatic Science and Technology (Eawag). The research concept aims at assessing the complex interactions within the arsenic-iron-phosphate-system under field conditions at a study site next to the Red River. First, filtration experiments using local groundwater enriched in As and PO43- will be used to determine the As adsorption capacity of different and previously geochemically characterized iron(oxyhydr)oxides. In a second step, sample carrier containing As loaded iron(oxyhydr)oxides will be introduced into surface near aquifer parts of the study site (via existing groundwater monitoring wells). These samples will be exposed to local groundwater characterized by increased As, Fe2+ and PO43- concentrations for the following nine months. Using the in situ exposition of predefined iron(oxyhydr)oxides, it will be possible to distinguish potential mineral transformations and their influences on the As immobilization capacity of the respective iron(oxyhydr)oxides. By combining the results and outcomes of the field experiments, new and important conclusions regarding the mobility of As can be drawn. The data can be used to create a hydrochemical transport model describing reactive As transport within the investigation area. In addition, the results of the in situ exposition experiments will allow to draw conclusions in respective to the long term As immobilization capacity of different iron(oxyhydr)oxides, which is an essential information regarding in situ decontamination techniques.
Sandy soils of the arid/semiarid dune fields of the Palestinian Gaza Strip and the Israeli western Negev are extensively covered by biological soil crusts (BSC), which stabilize the surface and prevent desertification. Political discussions in Israel suggest transferring a large part of this sand belt to the Gaza Strip within a final peace accord. Inappropriate land uses may lead to destruction of the BSC and initiate desertification, as already occurring in parts of the Gaza Strip. In this interdisciplinary project the influence of environmental factors on the vitality, stability and the recovery potential of the BSC will be investigated in order to evaluate the carrying capacity of this fragile landscape, in relation to rainfall, soil and relief conditions. A transect stretching from the Mediterranean coast in the Palestinian Gaza Strip (370 mm rainfall) to 65 km southwards in Israel ( Nizzana , less than 100 mm rainfall) has been selected. The interactions of molecular biological, physiological, physical and soil chemical processes, expressed in specific characteristics of the BSC and the underlying soil, will be assessed from the molecular to the landscape scale.
Evidence is compelling for a positive correlation between urbanisation and increment of allergic sensitisation and diseases. The reason for this association is not clear to date. Some data point to a pro-allergic effect of anthropogenic factors on susceptible individuals. Data analysing the impact of environmental - natural and anthropogenic - factors on the allergenicity of allergen carriers such as pollen grains are scarce, and if applicable only taken from in vitro experimental designs. This study will analyse one of the most common allergy inducers in northern Europe - the birch pollen. Under natural exposure conditions, birch pollen will be analysed with respect to their allergenicity. Within an interdisciplinary research team this study will evaluate the effect of natural (e.g. soil, climate, genetic background) and anthropogenic (e.g. traffic pollutants) factors on birch pollen in a holistic approach including analysis of allergen bioavailability, release of pollen associated lipid mediators from birch pollen grains, in vitro immunostimulatory activity and in vivo allergenic potential. These data collected in the time course of three years will significantly add to our understanding how urbanisation and climate change influence the allergenicity of birch pollen and will help us in the future to set up primary prevention studies.
Sediment erosion and transport is critical to the ecological and commercial health of aquatic habitats from watershed to sea. There is now a consensus that microorganisms inhabiting the system mediate the erosive response of natural sediments ('ecosystem engineers') along with physicochemical properties. The biological mechanism is through secretion of a microbial organic glue (EPS: extracellular polymeric substances) that enhances binding forces between sediment grains to impact sediment stability and post-entrainment flocculation. The proposed work will elucidate the functional capability of heterotrophic bacteria, cyanobacteria and eukaryotic microalgae for mediating freshwater sediments to influence sediment erosion and transport. The potential and relevance of natural biofilms to provide this important 'ecosystem service' will be investigated for different niches in a freshwater habitat. Thereby, variations of the EPS 'quality' and 'quantity' to influence cohesion within sediments and flocs will be related to shifts in biofilm composition, sediment characteristics (e.g. organic background) and varying abiotic conditions (e.g. light, hydrodynamic regime) in the water body. Thus, the proposed interdisciplinary work will contribute to a conceptual understanding of microbial sediment engineering that represents an important ecosystem function in freshwater habitats. The research has wide implications for the water framework directive and sediment management strategies.
During microbial turnover of organic chemicals in soil, non-extractable residues (NER) are formed frequently. Studies on NER formation usually performed with radioisotope labelled tracer compounds are limited to localisation and quantitative analyses but their chemical composition is left unknown. Recently, we could show for 2,4-dichlorophenoxyacetic acid and ibuprofen that during microbial turnover in soil nearly all NER were derived from microbial biomass, since degrading bacteria use the pollutant carbon for their biomass synthesis. Their cell debris is subsequently stabilised within soil organic matter (SOM) forming biogenic NER (bioNER). It is still unknown whether bioNER are also formed during biodegradation of other, structurally different compound classes of organic contaminants. Therefore, agricultural soil will be incubated with labelled compounds of five classes of commonly used and emerging pesticides: organophosphate, phenylurea, triazinone, benzothiadiazine and aryloxyphenoxypropionic acid. The fate of the label will be monitored in both living and non-living SOM pools and the formation of bioNER will be quantified for each compound over extended periods of time. In addition, soil samples from long-term lysimeter studies with 14C-labelled pesticide residues (e.g. triazine, benzothiazole and phenoxypropionic acid group) will be also analysed for bioNER formation. The results will be summarised to identify the metabolic conditions of microorganisms needed for bioNER formation and to develop an extended concept of risk assessment including bioNER formation in soils.
Dissolved organic matter (DOM) is one major source of subsoil organic matter (OM). P5 aims at quantifying the impact of DOM input, transport, and transformation to the OC storage in the subsoil environment. The central hypotheses of this proposal are that in matric soil the increasing 14C age of organic carbon (OC) with soil depth is due to a cascade effect, thus, leading to old OC in young subsoil, whereas within preferential flowpaths sorptive stabilization is weak, and young and bioa-vailable DOM is translocated to the subsoil at high quantities. These hypotheses will be tested by a combination of DOC flux measurements with the comparative analysis of the composition and the turnover of DOM and mineral-associated OM. The work programme utilizes a DOM monitoring at the Grinderwald subsoil observatory, supplemented by defined experiments under field and labora-tory conditions, and laboratory DOM leaching experiments on soils of regional variability. A central aspect of the experiments is the link of a 13C-leaf litter labelling experiment to the 14C age of DOM and OM. With that P5 contributes to the grand goal of the research unit and addresses the general hypotheses that subsoil OM largely consists of displaced and old OM from overlying horizons, the sorption capacity of DOM and the pool size of mineral-associated OM are controlled by interaction with minerals, and that preferential flowpaths represent 'hot spots' of high substrate availability.
Organotin and especially butyltin compounds are used for a variety of applications, e.g. as biocides, stabilizers, catalysts and intermediates in chemical syntheses. Tributyltin (TBT) compounds exhibit the greatest toxicity of all organotins and have even been characterized as one of the most toxic groups of xenobiotics ever produced and deliberately introduced into the environment. TBT is not only used as an active biocidal compound in antifouling paints, which are designed to prevent marine and freshwater biota from settlement on ship hulls, harbour and offshore installations, but also as a biocide in wood preservatives, textiles, dispersion paints and agricultural pesticides. Additionally, it occurs as a by-product of mono- (MBT) and dibutyltin (DBT) compounds, which are used as UV stabilizer in many plastics and for other applications. Triphenyltin (TPT) compounds are also used as the active biocide in antifouling paints outside Europe and furthermore as an agricultural fungicide since the early 1960s to combat a range of fungal diseases in various crops, particularly potato blight, leaf spot and powdery mildew on sugar beet, peanuts and celery, other fungi on hop, brown rust on beans, grey moulds on onions, rice blast and coffee leaf rust. Although the use of TBT and TPT was regulated in many countries world-wide from restrictions for certain applications to a total ban, these compounds are still present in the environment. In the early 1970s the impact of TBT on nontarget organisms became apparent. Among the broad variety of malformations caused by TBT in aquatic animals, molluscs have been found to be an extremely sensitive group of invertebrates and no other pathological condition produced by TBT at relative low concentrations rivals that of the imposex phenomenon in prosobranch gastropods speaking in terms of sensitivity. TBT induces imposex in marine prosobranchs at concentrations as low as 0,5 ng TBT-Sn/L. Since 1993, for the littorinid snail Littorina littorea a second virilisation phenomenon, termed intersex, is known. In female specimens affected by intersex the pallial oviduct is transformed of towards a male morphology with a final supplanting of female organs by the corresponding male formations. Imposex and intersex are morphological alterations caused by a chronic exposure to ultra-trace concentrations of TBT. A biological effect monitoring offers the possibility to determine the degree of contamination with organotin compounds in the aquatic environment and especially in coastal waters without using any expensive analytical methods. Furthermore, the biological effect monitoring allows an assessment of the existing TBT pollution on the basis of biological effects. Such results are normally more relevant for the ecosystem than pure analytical data. usw.
The sorption of anions in geotechnical multibarrier systems of planned high level waste repositories (HLWR) and of non-ionic and organic pollutants in conventional waste disposals are in the center of recent research. In aquatic systems, persistent radionuclides such as 79Se, 99Tc, 129I exist in a form of anions. There is strongly increasing need to find materials with high sorption capacities for such pollutants. Specific requirements on barrier materials are long-term stability of adsorbent under various conditions such as T > 100 C, varying hydrostatic pressure, and the presence of competing ions. Organo-clays are capable to sorb high amounts of cations, anions and non-polar molecules simultaneously having selectivity for certain ions. This project is proposed to improve the understanding of sorption and desorption processes in organo-clays. Additionally, the modification of material properties under varying chemical and thermal conditions will be determined by performing diffusion and advection experiments. Changes by sorption and diffusion will be analyzed by determining surface charge and contact angles. Molecular simulations on models of organo-clays will be conducted in an accord with experiments with aim to understand and analyze experimental results. The computational part of the project will profit from the collaboration of German partner with the group in Vienna, which has a long standing experience in a modeling of clay minerals.
Water, carbon and nitrogen are key elements in all ecosystem turnover processes and they are related to a variety of environmental problems, including eutrophication, greenhouse gas emissions or carbon sequestration. An in-depth knowledge of the interaction of water, carbon and nitrogen on the landscape scale is required to improve land use and management while at the same time mitigating environmental impact. This is even more important under the light of future climate and land use changes.In the frame of the proposal 'Uncertainty of predicted hydro-biogeochemical fluxes and trace gas emissions on the landscape scale under climate and land use change' we advocate the development of fully coupled, process-oriented models that explicitly simulate the dynamic interaction of water, carbon and nitrogen turnover processes on the landscape scale. We will use the Catchment Modelling Framework CMF, a modular toolbox to implement and test hypothesis of hydrologic behaviour and couple this to the biogeochemical LandscapeDNDC model, a process-based dynamic model for the simulation of greenhouse gas emissions from soils and their associated turnover processes.Due to the intrinsic complexity of the models in use, the predictive uncertainty of the coupled models is unknown. This predictive (global) uncertainty is composed of stochastic and structural components. Stochastic uncertainty results from errors in parameter estimation, poorly known initial states of the model, mismatching boundary conditions or inaccuracies in model input and validation data. Structural uncertainty is related to the flawed or simplified description of natural processes in a model.The objective of this proposal is therefore to quantify the global uncertainty of the coupled hydro-biogeochemical models and investigate the uncertainty chain from parameter uncertainty over forcing data uncertainty up the structural model uncertainty be setting up different combinations of CMF and LandscapeDNDC. A comprehensive work program has been developed structured in 4 work packages, that consist of (1) model set up, calibration and uncertainty assessment on site scale followed by (2) an application and uncertainty assessment of the coupled model structures on regional scale, (3) global change scenario analyses and finally (4) evaluating model results in an ensemble fashion.Last but not least, a further motivation of this proposal is to provide project results in a manner that they support planning and decision taking under uncertainty, as this proposal is part of the package proposal on 'Methodologies for dealing with uncertainties in landscape planning and related modelling'.
The broad objective of the research is to gain a fundamental understanding of the surface reaction chemistry of exhaust catalysts operating under cycling conditions. Using an integrated theoretical approach we specifically target NOx abatement, with particular emphasis on the appearance and destruction of surface oxide phases as the reactor conditions cycle from oxidative to reductive during the operation of the NOx Storage Reduction (NSR) catalyst system. Methodologically this requires material-specific, quantitative and explicitly time-dependent simulation tools that can follow the evolution of the system over the macroscopic time-scales of NSR cycles, while simultaneously accounting for the atomic-scale site heterogeneity and spatial distributions at the evolving surface. To meet these challenging demands we will develop a novel multi-scale methodology relying on a multi-lattice first-principles kinetic Monte Carlo (kMC) approach. As representative example the simulations will be carried out on a PdO(101)/Pd(100) surface oxide model, but care will be taken to ensure a generalization of the multi-lattice first-principles kMC approach to other systems in which phase transformations may occur and result in a change in the surface lattice structure depending upon environmental variables.
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